CN113322072B

CN113322072B - Compatible ITO etching solution and preparation method thereof

Info

Publication number: CN113322072B
Application number: CN202110708889.9A
Authority: CN
Inventors: 戈烨铭; 何珂; 汤晓春
Original assignee: JIANGYIN RUNMA ELECTRONIC MATERIAL CO Ltd
Current assignee: JIANGYIN RUNMA ELECTRONIC MATERIAL CO Ltd
Priority date: 2021-06-25
Filing date: 2021-06-25
Publication date: 2022-06-03
Anticipated expiration: 2041-06-25
Also published as: CN113322072A

Abstract

The invention relates to a compatible ITO etching solution and a preparation method thereof, wherein the raw materials of the etching solution comprise, by weight, 10% -30% of nitric acid, 10% -20% of sulfuric acid, 1% -10% of metal salt, 0.5% -3% of ammonium salt and the balance of pure water; and adding nitric acid, pure water, metal salt and ammonium salt in sequence, fully stirring and uniformly mixing, slowly adding sulfuric acid into the uniformly mixed mixture of nitric acid, pure water, metal salt and ammonium salt, and fully stirring and uniformly mixing to obtain the compatible ITO etching solution. The compatible ITO etching solution is suitable for ITO film layers with different thicknesses, and has mild and stable reaction and high etching precision. Aiming at the film layers with different thicknesses, the purpose of etching can be achieved only by adjusting the etching time, and the components of the etching solution do not need to be replaced and the content of the components of the etching solution does not need to be adjusted.

Description

Compatible ITO etching solution and preparation method thereof

Technical Field

The invention belongs to the technical field of etching solutions, and particularly relates to a compatible ITO etching solution and a preparation method thereof.

Background

The Indium Tin Oxide (ITO) conductive film is manufactured by plating a layer of indium tin oxide film on soda-lime-based or silicon-boron glass by a magnetron sputtering method. The ITO conductive film has low resistivity, high visible light transmittance, high infrared reflection, excellent adhesion to a substrate, scratch resistance and the like, and is widely applied to the panel display industry. In order to prepare a desired electrode pattern, wet etching of the ITO conductive film is generally required. The ITO etching solution used in the existing industry as a panel process usually adopts a hydrochloric acid/nitric acid mixed aqueous solution, a hydrochloric acid/ferric trichloride aqueous solution, an iodic acid aqueous solution, a phosphoric acid aqueous solution and the like, and the etching solutions have strong corrosion capability, and in the etching process, the etching angle and the etching time are often difficult to control, and the etching precision is difficult to control.

Chinese patent CN201210206045.5 discloses a novel aqua regia system ITO etching solution and a preparation method thereof, the ITO etching solution comprises hydrochloric acid, nitric acid, pure water and additives, wherein the additives comprise nitrate compounds, chlorine-based compounds and surfactants, the etching solution has strong etching capability, in the etching process, it is often difficult to control the etching angle and etching time, and it is not suitable for ITO film layers with small thickness, and the preparation process of the etching solution is complicated.

Chinese patent CN201510832036.0 discloses an ITO etching solution for advanced flat plates, which comprises the following components by weight: 4-16% of sulfuric acid, 7-22% of nitric acid, 0.1-10% of acetic acid, 0.01-5% of additive and the balance of water, and adopts a sulfuric acid/nitric acid/acetic acid triacid ITO etching system, so that the content of the used acid is high, the etching reaction is severe, the etching precision is difficult to control, the method is not suitable for ITO film layers with small thickness, and the cost of the etching solution is high.

Therefore, a compatible ITO etching solution suitable for ITO films with different thicknesses and capable of ensuring etching accuracy is needed, and only the etching time needs to be controlled without switching the etching solution in the etching process.

Disclosure of Invention

The invention aims to provide a compatible ITO etching solution which is suitable for ITO film layers with different thicknesses, and has mild and stable reaction and high etching precision.

The technical scheme adopted by the invention for solving the problems is as follows: the compatible ITO etching solution comprises, by weight, 10% -30% of nitric acid, 10% -20% of sulfuric acid, 1% -10% of metal salt, 0.5% -3% of ammonium salt and the balance of pure water.

Furthermore, the raw materials of the etching solution comprise, by weight, 15% of nitric acid, 10% of sulfuric acid, 5% of metal salt, 0.5% of ammonium salt, and the balance of pure water.

Further, the nitric acid is of electronic grade, and the concentration of the nitric acid is 71% wt.

Further, the sulfuric acid is electronic grade, and the concentration of the sulfuric acid is 98% wt.

Further, the metal salt is any one or more of lithium nitrate, lithium acetate, sodium nitrate, sodium acetate, sodium phosphate, potassium phosphate and potassium acetate.

Further, the metal salt is sodium acetate.

Further, the ammonium salt is at least one of ammonium fluoride, ammonium bifluoride, ammonium chloride and ammonium bifluoride.

Further, the ammonium salt is ammonium fluoride.

The invention also aims to provide a preparation method of the compatible ITO etching solution, which comprises the following steps:

(1) the nitric acid, the sulfuric acid, the metal salt and the ammonium salt are respectively weighed according to the weight percentage of 10-30%, 10-20%, 1-10% and 0.5-3%, and the balance is pure water.

(2) Adding nitric acid, pure water, metal salt and ammonium salt in turn into a batching tank, fully stirring and uniformly mixing.

(3) And slowly adding sulfuric acid into the uniformly mixed mixture of nitric acid, pure water, metal salt and ammonium salt, fully stirring, and uniformly mixing to obtain the compatible ITO etching solution.

Further, the stirring is mechanical stirring or magnetic stirring.

Further, the stirring is carried out at normal temperature and normal pressure, and the stirring speed is 50-100 r/min.

Compared with the prior art, the invention has the advantages that:

(1) the etching solution is suitable for ITO film layers with different thicknesses (400-1000A), the reaction is mild and stable, the etching precision is high, and more preferentially, the content of nitric acid needs to be controlled to be 10% -30%, the content of sulfuric acid needs to be controlled to be 10% -20%, the content of metal salt needs to be controlled to be 1% -10%, the content of ammonium salt needs to be controlled to be 0.5% -3%, and stable and uniform etching of ITO film layers with different thicknesses can be realized; aiming at the film layers with different thicknesses, the purpose of etching can be achieved only by adjusting the etching time, and the components of the etching solution do not need to be replaced and the content of the components of the etching solution does not need to be adjusted.

(2) According to the invention, the metal salt and the ammonium salt are added simultaneously, and have a synergistic effect, so that the etching speed is controlled, the requirement of controlling the etching angle is further realized, and the defects of severe etching reaction and difficulty in controlling the etching precision are avoided.

(3) The etching solution disclosed by the invention is not only suitable for etching an ITO film layer, but also suitable for etching an Indium Gallium Zinc Oxide (IGZO) film layer, and is especially suitable for etching an IGZO film layer with the thickness of 1000A.

Detailed Description

The present invention will be described in further detail with reference to examples.

Example 1

The compatible ITO etching solution comprises, by weight, 15% of nitric acid, 10% of sulfuric acid, 5% of sodium acetate, 0.5% of ammonium fluoride and the balance of pure water.

A preparation method of a compatible ITO etching solution comprises the following steps:

(1) the nitric acid, the sulfuric acid, the sodium acetate, the ammonium fluoride and the pure water are respectively weighed and reconfigured according to the weight percentage.

(2) Adding nitric acid, pure water, sodium acetate and ammonium fluoride in turn into a proportioning tank, fully stirring and uniformly mixing.

(3) And slowly adding sulfuric acid into the uniformly mixed mixture of nitric acid, pure water, sodium acetate and ammonium fluoride, fully stirring, and uniformly mixing to obtain the compatible ITO etching solution.

Wherein the stirring is mechanical stirring at normal temperature and normal pressure, and the stirring speed is 80 r/min.

Example 2

The compatible ITO etching solution comprises, by weight, 20% of nitric acid, 15% of sulfuric acid, 5% of lithium nitrate, 1% of ammonium chloride and the balance of pure water.

(1) the nitric acid, the sulfuric acid, the lithium nitrate, the ammonium chloride and the pure water are respectively weighed and reconfigured according to the weight percentage.

(2) Adding nitric acid, pure water, lithium nitrate and ammonium chloride in turn into a proportioning tank, fully stirring and uniformly mixing.

(3) And slowly adding sulfuric acid into the uniformly mixed mixture of nitric acid, pure water, lithium nitrate and ammonium chloride, fully stirring, and uniformly mixing to obtain the compatible ITO etching solution.

Wherein the stirring is mechanical stirring at normal temperature and normal pressure, and the stirring speed is 100 r/min.

Example 3

The compatible ITO etching solution comprises, by weight, 15% of nitric acid, 15% of sulfuric acid, 3% of sodium acetate, 1.5% of ammonium bifluoride and the balance of pure water.

(1) the nitric acid, the sulfuric acid, the sodium acetate, the ammonium bifluoride and the pure water are respectively weighed and reconfigured according to the weight percentage.

(2) Adding nitric acid, pure water, sodium acetate and ammonium bifluoride in turn into a batching tank, fully stirring and uniformly mixing.

(3) And slowly adding sulfuric acid into the uniformly mixed mixture of nitric acid, pure water, sodium acetate and ammonium bifluoride, fully stirring, and uniformly mixing to obtain the compatible ITO etching solution.

Comparative example 1

The only difference from example 1 is: no sodium acetate was added.

Comparative example 2

The only difference from example 1 is: no ammonium fluoride was added.

The ITO etching solution prepared in example 1 was used to etch ITO film layers and IGZO film layers with different thicknesses, wherein the etching temperature was 40 ℃, and the etching results are shown in the following table:

note: the target requirements of the ITO etching solution are as follows: CD lose: the single side is less than or equal to 0.25 mu m, the Taper angle is less than 50 degrees, and no residue is left.

As seen from the above table, the ITO etching solution prepared in embodiment 1 can stably and uniformly etch ITO films with different thicknesses, and for the films with different thicknesses, the etching purpose can be achieved only by adjusting the etching time without changing the components of the etching solution and adjusting the content of the components of the etching solution.

The ITO etching solutions prepared in examples 1-3 and comparative examples 1-2 were used to etch different ITO film layers at an etching temperature of 40 ℃ and the etching results are shown in the following table:

as can be seen from the above table, compared with the ITO etching solutions of examples 1 to 3, the ITO etching solutions prepared without adding sodium acetate and without adding ammonium fluoride have poorer etching precision, and from the etching results of comparative examples 1 to 2 and examples 1 to 3, that is, from the etching effects of adding only sodium acetate, only ammonium fluoride and simultaneously adding sodium acetate and ammonium fluoride, the actual etching effect of simultaneously adding sodium acetate and ammonium fluoride is significantly greater than the expected etching effect (the sum of the etching effects of adding only sodium acetate and only ammonium fluoride), and the metal salt and the ammonium salt of the present invention have a synergistic effect, but are not a simple additive effect of the two.

In addition to the above embodiments, the present invention also includes other embodiments, and any technical solutions formed by equivalent transformation or equivalent replacement should fall within the scope of the claims of the present invention.

Claims

1. A compatible ITO etching solution is characterized in that: the etching solution comprises, by weight, 10-30% of nitric acid, 10-20% of sulfuric acid, 1-10% of metal salt, 0.5-3% of ammonium salt and the balance of pure water; the metal salt is sodium acetate, and the ammonium salt is ammonium fluoride.

2. The compatible ITO etchant of claim 1, wherein: the raw materials of the etching solution comprise, by weight, 15% of nitric acid, 10% of sulfuric acid, 5% of metal salt, 0.5% of ammonium salt and the balance of pure water.

3. The compatible ITO etchant of claim 1, wherein: the nitric acid is electronic grade, and the concentration of the nitric acid is 71 wt%.

4. The compatible ITO etchant of claim 1, wherein: the sulfuric acid is of electronic grade, and the concentration of the sulfuric acid is 98 wt%.

5. A method for preparing the compatible ITO etchant according to any one of claims 1 to 4, wherein the compatible ITO etchant comprises: the method comprises the following steps:

(1) weighing and preparing 10-30 wt% of nitric acid, 10-20 wt% of sulfuric acid, 1-10 wt% of metal salt and 0.5-3 wt% of ammonium salt, and the balance of pure water;

(2) sequentially adding nitric acid, pure water, metal salt and ammonium salt into a batching tank, fully stirring and uniformly mixing;

6. The method for preparing the compatible ITO etching solution according to claim 5, wherein: the stirring is mechanical stirring or magnetic stirring, the stirring is carried out at normal temperature and normal pressure, and the stirring speed is 50-100 r/min.